WO2012016835A2 - Liquides ioniques présentant une certaine teneur en polymères ioniques - Google Patents

Liquides ioniques présentant une certaine teneur en polymères ioniques Download PDF

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WO2012016835A2
WO2012016835A2 PCT/EP2011/062431 EP2011062431W WO2012016835A2 WO 2012016835 A2 WO2012016835 A2 WO 2012016835A2 EP 2011062431 W EP2011062431 W EP 2011062431W WO 2012016835 A2 WO2012016835 A2 WO 2012016835A2
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cations
ionic liquid
compound
groups
acid
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WO2012016835A3 (fr
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Aurelie Alemany
Dirk Gerhard
Bolette Urtel
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Basf Se
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Priority to EP11733883.0A priority patent/EP2598593B1/fr
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Publication of WO2012016835A3 publication Critical patent/WO2012016835A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/047—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for absorption-type refrigeration systems
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/2203—Heterocyclic nitrogen compounds used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/223—Five-membered rings containing nitrogen and carbon only
    • C10M2215/224—Imidazoles
    • C10M2215/2245—Imidazoles used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/0406—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/101—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2221/00—Organic macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2221/02—Macromolecular compounds obtained by reactions of monomers involving only carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/077—Ionic Liquids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/08—Hydraulic fluids, e.g. brake-fluids

Definitions

  • the present invention relates to methods for adjusting the viscosity of a salt having a melting point of less than 100 ° C at atmospheric pressure (abbreviated to ionic liquid), which is characterized in that the ionic liquid is added to an oligomeric or polymeric compound having a content of at least 0 , 01 mole covalently bound acid groups / 100g compound, wherein at least 1% of the acid groups are present as salt with an organic cation containing at least one heteroatom selected from nitrogen, oxygen, sulfur or phosphorus.
  • ionic liquid a salt having a melting point of less than 100 ° C at atmospheric pressure
  • Ionic liquids are of great interest for a wide variety of technical applications.
  • applications as a solvent or electrolyte are applications as a lubricant, hydraulic fluid or operating fluid, as a heat carrier, for heat transfer or as a sealing or Absperrroughkeit into consideration.
  • ionic liquids as absorbents in heat pumps, i. as operating fluid, is e.g. from WO 2005/1 13702 known.
  • ionic liquids as a hydraulic fluid, lubricant, operating fluid, stop-off or sealing fluid are e.g. also listed in WO 2006/087333. From the earlier, not previously published EP application 09169389.5 (PF 62527), inter alia, the addition of ionic compounds for adjusting the viscosity of ionic liquids is described.
  • suitable ionic liquids must meet a variety of required properties.
  • An essential feature in all these applications is the viscosity. Often many, but not all, of the required properties are met by a selected ionic liquid. The remaining, unfulfilled properties must, if possible, be adjusted accordingly. Thus, e.g. for an intended use, the viscosity of the otherwise suitable ionic liquid may not be high enough.
  • the subject of the process according to the invention is the adjustment of the viscosity of an ionic liquid by adding a compound.
  • the ionic liquid is a salt with a melting point of less than 100 ° C at 1 bar.
  • the ionic liquid has a melting point less than 70 ° C and more preferably less than 30 ° C.
  • the ionic liquid is liquid under normal conditions (1 bar, 21 ° C).
  • the ionic liquid is a salt and therefore consists of at least one cation and at least one anion.
  • Preferred ionic liquids contain at least one organic compound as cation, very particularly preferably they contain only organic compounds as cations.
  • Suitable organic cations are, in particular, organic compounds containing heteroatoms, such as nitrogen, sulfur, oxygen or phosphorus, particularly preferably organic compounds having a cationic group selected from an ammonium group, an oxonium group, a sulfonium group or a phosphonium group.
  • the ionic liquids are ammonium cation salts, which includes non-aromatic compounds having a localized positive charge on the nitrogen atom, e.g. Compounds with terminated nitrogen (quaternary ammonium compounds) or compounds with trivalent nitrogen, wherein a bond is a double bond, or aromatic compounds with delocalized positive charge and at least one, preferably one or two nitrogen atoms in the ring system are understood.
  • organic cations are quaternary ammonium cations with preferably three or four aliphatic substituents, particularly preferably C 1 - to C 12 -alkyl groups, on the nitrogen atom.
  • Organic cations which contain a heterocyclic ring system having one or two nitrogen atoms as part of the ring system are also particularly preferred.
  • Suitable compounds are monocyclic, bicyclic, aromatic or non-aromatic ring systems. Examples include bicyclic systems, as described in WO 2008/043837.
  • bicyclic systems of WO 2008/043837 are diazabicyclo derivatives, preferably of a 7- and a 6-ring, which contain an amidinium group; Particular mention may be made of the 1,8-diazabicyclo (5.4.0) undec-7-enium cation.
  • Very particularly preferred organic cations comprise a heterocyclic ring system, preferably a five- or six-membered heterocyclic ring system, with one or two nitrogen atoms as constituent of the heterocyclic ring system.
  • Suitable cations are e.g. Pyridinium cations, pyridazinium cations, pyrimidinium cations, pyrazinium cations, imidazolium cations, pyrazolium cations, pyrazolinium cations, imidazolinium cations, thiazolium cations, triazolium cations, pyrrolidinium cations and imidazolidinium cations. These cations are e.g. in WO 2005/1 13702.
  • the nitrogen atoms are in each case by an H atom or preferably an organic group having generally not more than 20 C atoms, preferably a hydrocarbon group, in particular a C1 to C16 alkyl group, in particular a C1 to C10, particularly preferably a C1 to C4 alkyl groups substituted.
  • the carbon atoms of the ring system can also be substituted by organic groups having generally not more than 20 carbon atoms, preferably a hydrocarbon group, in particular a C1 to C16 alkyl group, in particular a C1 to C10, more preferably a C1 to C4 alkyl groups.
  • ammonium cations are quaternary ammonium cations, imidazolium cations, pyrimidinium cations and pyrazolium cations.
  • imidazolium cations in particular imidazolium cations of the formula I.
  • R 1 and R 3 independently of one another represent an H atom or an organic group having 1 to 20 C atoms
  • R2, R4, and R5 independently represent an H atom or an organic group having 1 to 20 C atoms.
  • R1 to R5 have the preferred meanings as given below for formula II
  • the anion may be an organic or inorganic anion.
  • Suitable anions are, in particular, those from the group of halides and halogen-containing compounds of the formulas:
  • M is a metal and Hal is fluorine, chlorine, bromine or iodine, r and t are integer positive numbers and indicate the stoichiometry of the complex and s is an integer positive number indicating the charge of the complex; the group of sulfides, hydrogen sulfides, polysulfides, hydrogen polysulfides and thiolates of the general formulas:
  • R a , R b , R c and R d are each independently
  • 1-pentyl 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl, 3-methyl-3 pentyl, 2,2-dimethyl-1-butyl, 2,3-dimethyl-1-butyl, 3,3-dimethyl-1-butyl,
  • C 3 -C 12 -cycloalkenyl and their aryl, heteroaryl, cycloalkyl, halogen, hydroxy, amino, carboxy, formyl, -O-, -CO- or -CO-O-substituted components, such as 3-cyclopentyl, 2-cyclohexenyl, 3-cyclohexenyl, 2,5-cyclohexadienyl or C q F 2 ( q -a) -3 (ib) H 2a-3b with q ⁇ 30, 0 ⁇ a ⁇ q and b 0 or 1;
  • R a , R b , R c and R d are preferably each independently a hydrogen atom or a C 1 to C 12 alkyl group.
  • Ra, Rb, Rc and Rd are preferably each independently a hydrogen atom or a C1 to C12 alkyl group.
  • Chloride Bromide; iodide; thiocyanate; hexafluorophosphate; Trifluoromethanesulfonate; methane; the carboxylates, in particular formate; Acetate; mandelate; Nitrate; Nitrite; trifluoroacetate; Sulfate; Bisulfate; Methyl sulfate; ethyl sulfate; 1-propyl sulfate; 1-butyl sulfate; 1 -hexyl sulfate; 1-octyl sulfate; Phosphate; dihydrogen phosphate; Hydrogen phosphate; C1-C4 dialkyl phosphates; propionate; tetrachloroaluminate; AI2CI7-; chlorozincate; Chloroferrat; imide, bis (trifluoromethylsulfonyl); Bis (pentafluoro
  • Anions are particularly preferably those from the group of alkyl sulfates
  • R a is a C 1 to C 12 alkyl group, preferably a C 1 -C 6 alkyl group, the alkyl sulfonates
  • R a is a C 1 to C 12 alkyl group, preferably a C 1 -C 6 alkyl group, of the halides, especially chloride and bromide and the pseudohalides, such as thiocyanate, dicyanamide, the carboxylates R a COO-;
  • R a is a C 1 to C 20 alkyl group, preferably a C 1 -C 8 alkyl group, in particular acetate, the phosphates,
  • dialkyl phosphates of the formula R a R b P0 4 - wherein R a and R b independently of one another represent a C 1 to C 6 alkyl group; in particular, R a and R b are the same alkyl group, which may be mentioned dimethyl phosphate and diethyl phosphate and the phosphonates, in particular the monoalkylphosphonic acid esters
  • R a R b P0 3 - wherein R a and R b independently of one another represent a C 1 to C 6 alkyl group.
  • Very particularly preferred anions are
  • Chloride bromide, hydrogensulfate, tetrachloroaluminate, thiocyanate, dicyanamide, methylsulfate, ethylsulfate, methanesulfonate, triflate (CF 3 S0 3 ), formate, acetate, dimethyl phosphate, diethyl phosphate, p-tolylsulfonate, tetrafluoroborate and hexafluorophosphate, methylmethylphosphonate and methylphosphonate.
  • these are anions which contain a sulfate or sulfonate group, in particular sulfates of the formula Z-SC - or sulfonates of the formula Z-S0 3 -, where Z is an organic group having 1 to 10 C atoms , preferably a C 1 - to C 10 -alkyl group or for fluorinated organic groups (triflate), and particularly preferably a methyl or ethyl group.
  • any mixtures of ionic liquids with triflate, alkyl sulfonates and / or alkyl sulfates as anion is often corrosion in contact with metals, such as steels, especially base steels, such as carbon-iron steels without further alloying constituents, to observe.
  • metals such as steels, especially base steels, such as carbon-iron steels without further alloying constituents
  • Particularly preferred ionic liquids consist exclusively of an organic cation having one of the above anions.
  • the molar weight of the ionic liquids is preferably less than 2000 g / mol, more preferably less than 1500 g / mol, more preferably less than 1000 g / mol, and most preferably less than 750 g / mol; in a particular embodiment, the molecular weight is between 100 and 750 or between 100 and 500 g / mol.
  • these are imidazolium compounds, particularly preferably imidazolium compounds of the formula II
  • R1 and R3 independently of one another represent an H atom or an organic group having 1 to 20 C atoms
  • R2, R4, and R5 independently represent an H atom or an organic group having 1 to 20 C atoms
  • X represents an anion
  • n represents 1, 2, or 3.
  • R 1 and R 3 is an organic group, in particular both R 1 and R 3 are an organic group, in particular an organic group containing 1 to 10 C atoms. Most preferably, it is a hydrocarbon group which has no further heteroatoms, e.g. a saturated or unsaturated aliphatic group, an aromatic group or a hydrocarbon group having both aromatic and aliphatic components.
  • R1 and R3 independently represent a C1 to C10 alkyl group, a C1 to C10 alkenyl group, e.g. an allyl group, a phenyl group, a benzyl group; most preferably R1 and R3 independently represent a C1 to C4 alkyl group, e.g.
  • R2 is H atom or a C1 to C4 alkyl group, e.g. a methyl group, ethyl group, propyl group, i-propyl group or n-butyl group.
  • R2, R4 and R5 are H atoms.
  • n is preferably 1.
  • Suitable anions X and preferred anions X are those listed above.
  • suitable ionic liquids are e.g. called such as a cation
  • ionic liquids which may be mentioned are: 1,3-dimethylimidazolium methylsulfate, 1,3-dimethylimidazolium ethylsulfate, 1,3-dimethylimidazolium hydrogensulfate, 1,3-dimethylimidazolium dimethyl phosphate, 1,3-dimethylimidazolium acetate, 1 , 3-dimethylimidazolium methanesulfonate, 1,3-dimethylimidazolium ethanesulfonate, 1,3-dimethylimidazolium triflate, 1,3-diethylimidazolium methylsulfate, 1,3-diethylimidazolium ethylsulfate, 1,3-diethylimidazolium bisulfate, 1, 3 Diethylimidazolium dimethyl phosphate, 1, 3 diethylimidazolium acetate, 1, 3-diethylim
  • the viscosity of the ionic liquid is adjusted by adding an oligomeric or polymeric compound.
  • the oligomeric or polymeric compound has a content of at least 0.01 mol, preferably at least 0.05 mol, particularly preferably at least 0.1 mol, in particular at least 0.2 mol and in a particular embodiment at least 0.3 mol of covalently bonded acid groups 100g of the compound.
  • the upper limit of the content of these acid groups is determined by the theoretically maximum possible content; in general, this content is not larger than 1.4 mol, which is e.g. is almost reached in the polyacrylic acid, in particular not greater than 1, 2 mol per 100g of compound.
  • the acid groups are e.g. to carboxylic acid groups, sulfonic acid groups or phosphonic acid groups. Preferred are carboxylic acid groups and sulfonic acid groups.
  • the oligomeric or polymeric compound is e.g. a polycondensate, a polyadduct or a polymer obtainable by free-radical polymerization, which accordingly consists at least partially of repeating units. Accordingly, the oligomeric or polymeric compound generally contains on average at least 4, in particular at least 10, acid groups in the molecule.
  • the compound may, for example, have a molecular weight of e.g. 300g / mol to 250,000 g / mol.
  • Preferred compounds have a molecular weight of at least 500, most preferably of at least 1,000 or else of at least 5,000 g / mol. In general, the molecular weight is at most 200,000, in particular at most 150,000 g / mol. Examples include compounds having a molecular weight of 10,000 to 150,000 or 30,000 to 120,000 g / mol. In the above information on the molecular weight, the associated cations are not taken into account. The above molecular weight is the number average molecular weight Mn which can be determined by known methods such as gel permeation chromatography or end group determination.
  • the acid groups of the oligomeric or polymeric compound are present at least partially or completely as a salt with the above organic cation, ie carboxylic acid groups are wholly or partially present as carboxylates and sulfonic acid wholly or partially as sulfonates.
  • carboxylic acid groups are wholly or partially present as carboxylates and sulfonic acid wholly or partially as sulfonates.
  • at least 10%, in particular at least 20% or at least 50%, of the acid groups are present as salt with the organic cation.
  • more than 80%, in particular 100%, of the acid groups are present as salt with the organic cation.
  • the oligomeric or polymeric compound may be solid or liquid at room temperature (21 ° C).
  • Preferred oligomeric or polymeric compounds are homogeneously miscible with water at 21 ° C. (1 bar) or have a solubility of at least 20 g, preferably at least 30 g of compound in 100 g of water at 21 ° C. (1 bar) in water.
  • preferred oligomeric or polymeric compounds are mentioned.
  • Suitable compounds having sulfonic acid groups are polystyrenesulfonic acid or styrenesulfonic acid copolymers which comprise at least 10% by weight, in particular at least 20% by weight or at least 50% by weight, of styrenesulfonic acid, where at least 1%, in particular at least 10 %, very particularly preferably at least 20% of the sulfonic acid groups are present as sulfonate groups with the organic cation.
  • Also suitable as compounds having sulfonic acid groups are poly-2-acrylamido-2-methylpropanesulfonic acid (poly-AMPS for short) or copolymers which contain at least 10% by weight, in particular at least 20% by weight or at least 50% by weight.
  • Organic cations which form a salt with the acid groups of the oligomeric or polymeric compound contain at least one heteroatom selected from nitrogen, sulfur, oxygen or phosphorus.
  • these are cations having a heterocyclic ring system, where the heteroatom (s) is nitrogen, sulfur, oxygen or phosphorus.
  • Suitable organic cations are compounds having a cationic group selected from an ammonium group, an oxonium group, a sulfonium group or a phosphonium group.
  • these are ammonium cations, which include non-aromatic cations with localized positive charge on the nitrogen atom, e.g. Compound fertilize with greedigem nitrogen (quaternary ammonium compounds) or cations with trivalent nitrogen, wherein a bond is a double bond, or aromatic cations are understood with delocalized positive charge and at least one, preferably one or two nitrogen atoms in the ring system.
  • Called e.g. quaternary ammonium cations having preferably three or four aliphatic substituents, particularly preferably C 1 - to C 12 -alkyl groups, on the nitrogen atom as organic cations.
  • organic cations which contain a heterocyclic ring system having at least one nitrogen atom, preferably one or two nitrogen atoms, as a constituent of the ring system.
  • Suitable compounds are monocyclic, bicyclic, aromatic or non-aromatic ring systems. Called e.g. bicyclic systems, as in
  • WO 2008/043837 are described.
  • the bicyclic systems of WO 2008/043837 are diazabicyclo derivatives, preferably of a 7- and a 6-ring, which contain an amidinium group; Particular mention may be made of the 1,8-diazabicyclo (5.4.0) undec-7-enium cation.
  • Very particularly preferred organic cations comprise a five- or six-membered heterocyclic ring system having one or two nitrogen atoms as a constituent of the heterocyclic ring system.
  • Suitable cations are pyridinium cations, pyridazinium cations, pyrimidinium cations, pyrazinium cations, imidazolium cations, pyrazolium cations, pyrazolinium cations, imidazolinium cations, thiazolium cations, triazolium cations, pyrrolidinium cations. Cations and imidazolidinium cations. These cations are listed, for example, in WO 2005/1 13702.
  • the nitrogen atoms are in each case by an H atom or preferably an organic group having generally not more than 20 C atoms, preferably a carbon atom.
  • hydrogen group in particular a C1 to C16 alkyl group, in particular a C1 to C10, particularly preferably a C1 to C4 alkyl groups substituted.
  • the carbon atoms of the ring system may also be substituted by organic groups having generally not more than 20 carbon atoms, preferably a hydrocarbon group, in particular a C1 to C16 alkyl group, in particular a C1 to C10, more preferably a C1 to C4 alkyl groups.
  • imidazolium cations particularly preferred are imidazolium cations, pyrimidinium cations and pyrazolium cations.
  • imidazolium cations are those of the formula I which corresponds to the imidazolium cation in the above formula II:
  • R1 to R5 have the above meaning given in formula II.
  • the cation of the ionic liquid is identical to the cation of the oligomeric or polymeric compound; in particular they may be identical imidazolium cations.
  • Poly (meth) acrylic acid or (meth) acrylic acid copolymers can be obtained by free-radical polymerization, in particular by solution or bulk polymerization, of acrylic acid or methacrylic acid and in the case of the copolymers of further free-radically polymerizable monomers.
  • Suitable (meth) acrylic acid copolymers are those with any desired comonomers, for example one or more comonomers selected from acrylates, vinyl esters, vinyl ethers, vinylaromatics, such as styrene, olefins, such as ethylene or propylene, or vinyl halides.
  • the comonomers may contain functional groups, for example those mentioned above as mandatory acid groups, acid amide groups or hydroxyl groups or other functional groups. Preference is given to poly (meth) acrylic acid or (meth) acrylic acid copolymers of acrylic acid or methacrylic acid with maleic acid or maleic anhydride.
  • Poly (meth) acrylic acid and (meth) acrylic acid copolymers are offered, for example, by BASF under the trademark Sokalan®.
  • the conversion of the acid groups into the corresponding salt groups with the organic cation can be carried out in a known manner.
  • the oligomeric or polymeric compound can be dissolved in a suitable solvent, for example water, and the desired organic cation can be added as a salt with a basic anion, for example hydroxide or methyl carbonate. It is a simple neutralization of the acid with the basic salt, while the acid groups are converted into the salt groups with the organic cation.
  • the solvent and the resulting neutralization product eg, water, methanol
  • the preparation of the oligomeric or polymeric compound by polymerization or copolymerization of the monomers can be carried out with salt groups. It should also be mentioned the possibility to polymerize monomers with acid groups in the presence of a basic salt of the organic cation, wherein the preparation of the compound and the conversion into the corresponding salt groups takes place in one step. For viscosity adjustment and the compositions
  • ionic liquid is also understood to mean a mixture of ionic liquids
  • compound is to be understood below also to mean a mixture of different oligomeric or polymeric compounds.
  • the oligomeric or polymeric compound is added to the ionic liquid preferably in an amount of from 0.1 to 35 parts by weight, more preferably from 0.1 to 30 parts by weight to 100 parts by weight, more preferably from 1 to 25 Parts by weight, in particular 1 to 20 parts by weight and most preferably added in amounts of 2 to 20 parts by weight, in particular from 2 to 15 parts by weight per 100 parts by weight of ionic liquid.
  • the compound is readily soluble in the ionic liquid, so that the resulting compositions are always homogeneous.
  • the addition of the compound increases the viscosity of the ionic liquid.
  • the compound can be added to the pure ionic liquid, but it can also be added to mixtures which contain other substances in addition to the ionic liquid; it may be e.g. to act substances such as solvents or substances dissolved in the ionic liquid. Such mixtures may e.g. during use of ionic liquids. It is therefore also an advantage of the method according to the invention that the
  • Viscosity even during the use of the ionic liquid can be increased or adjusted by adding the compound.
  • a further nonionic solvent to the ionic liquid. It is preferably a solvent which is homogeneously miscible with the ionic liquid at 21 ° C (1 bar) and at 21 ° C, 1 bar has a dielectric constant greater than 7.5.
  • Preferred solvents are polar aliphatic solvents with hydroxyl groups or ether groups.
  • Particularly preferred are water and methanol or mixtures thereof.
  • the amount of the nonionic solvent, in particular water or methanol, is preferably at least 1 part by weight, in particular at least 5 parts by weight, more preferably at least 10 parts by weight and very preferably at least 20 parts by weight per 100 weight Parts of ionic liquid.
  • the nonionic solvent may be added to the ionic liquid preferably in amounts of from 1 to 150 parts by weight, more preferably from 5 to 100% by weight, and most preferably from 10 to 80 parts by weight, especially from 20 to 60% by weight . Are added to 100 parts by weight of ionic liquid.
  • the temperature-dependence of the viscosity can be reduced, which is important for many applications with a wide temperature range.
  • the viscosity increase is still very clear even at high temperatures.
  • compositions containing an ionic liquid and the above compound can be obtained. Also obtainable are compositions containing an ionic liquid, the above compound and the above solvent.
  • compositions according to the invention may in particular contain other additives which are necessary or helpful in the intended use of the composition.
  • This can e.g. Corrosion inhibitors, defoamers, extreme pressure or anti-wear additives. Extremely pressure additives prevent the welding of 2 metallic materials under high pressure; anti-wear additives reduce abrasion or wear at high friction or stress.
  • compositions may contain more than 70% by weight, in particular more than 90% by weight and more preferably more than 95% by weight, more than 98% by weight or exclusively (100% by weight). %) from the ionic liquid, the oligomeric or polymeric Bond and possibly the solvent exist. This is especially the case before their use; During use, other substances may be included in the composition due to the nature of the use.
  • the viscosity of the composition when it is more than 90% by weight of the ionic liquid, the compound and the solvent, is preferably 10 mPa * s to 2,500 mPa * s at 20 ° C. The viscosity stated is the dynamic viscosity.
  • ionic liquid which may be an ionic liquid or a mixture of ionic liquids
  • 0.1 to 40 parts by weight in particular 0.5 to 30 parts by weight, particularly preferably 0.5 to 20 parts by weight of oligomeric or polymeric compound,
  • the composition of the invention contains non-ionic solvents in the minimum amounts specified above.
  • the composition of the invention is suitable for a variety of uses. Examples include uses as a lubricant, hydraulic fluid, operating fluid in devices, for example as an absorbent in thermodynamic cycle processes, which are based on absorption and desorption, as heat transfer, for heat transfer or as a sealing or Absperrteilkeit.
  • the compositions are homogeneous because the added oligomeric or polymeric compound dissolves well in the ionic liquid.
  • the compositions according to the invention already exhibit reduced corrosion without additional corrosion inhibitor.
  • the oligomeric or polymeric compound with the organic cations thus acts as a corrosion inhibitor and in many cases reduces corrosion, as often occurs in ionic liquids, especially ionic liquids with anions containing sulfate or sulfonate groups, in contact with metals, especially non-noble ones Steels, is observed.
  • EMIM-MeS0 3 EMIM-methylsulfonate
  • Poly-AMPS Poly-2-acrylamido-2-methylpropanesulfonic acid
  • the conversion of the acid groups of the polymeric compound into salt groups was carried out by reacting an aqueous solution of the respective polymer with 1-ethyl-3-methylimidazolium- hydroxide or with a quaternary ammonium salt (hydroxide of tetrabutylammonium Bu 4 N) The solvent was under reduced pressure and at elevated temperature removed. The acid groups were completely converted to the corresponding salt groups.
  • the polymers obtained with EM III as cations are designated as follows:
  • EMIM MeS0 3 + 3 wt.% EMIM polystyrenesulfonate Drops of a mixture of EMIM MeS0 3 + 3 wt.% EMIM polystyrenesulfonate and for comparison of EMIM MeS0 3 without additive were added to metal plates (base carbon steel, steel key 1 .0036). The metal plates were stored for 24 hours in air at 90 ° C in a drying oven, then the metal plates were cleaned with a solvent (ethanol and / or acetone) and assessed the corrosion optically. EMIM MeS0 3 alone resulted in significant, corrosive changes on the surface of the metal plate. For EMIM MeS0 3 + 3% by weight of EMIM polystyrenesulfonate, the surface showed no damage or color changes

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Physics & Mathematics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Detergent Compositions (AREA)

Abstract

La présente invention concerne un procédé permettant d'ajuster la viscosité d'un sel dont le point de fusion est inférieur à 100°C à pression normale (appelé liquide ionique), caractérisé en ce qu'on ajoute au liquide ionique un composé oligomère ou polymère dont la concentration en groupes acide à liaison covalente/100g de composé est d'au moins 0,01 mol, au moins 1% des groupes acide se présentant sous forme de sel avec un cation organique contenant au moins un hétéroatome choisi parmi l'azote, l'oxygène, le soufre ou le phosphore.
PCT/EP2011/062431 2010-07-26 2011-07-20 Liquides ioniques présentant une certaine teneur en polymères ioniques WO2012016835A2 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
ES11733883.0T ES2469373T3 (es) 2010-07-26 2011-07-20 Uso de líquidos iónicos con un contenido de pol�meros iónicos
EP11733883.0A EP2598593B1 (fr) 2010-07-26 2011-07-20 Utilisation de liquides ioniques présentant une certaine teneur en polymères ioniques

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EP10170775.0 2010-07-26
EP10170775 2010-07-26
EP11153466 2011-02-07
EP11153466.5 2011-02-07

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012163550A1 (fr) * 2011-06-03 2012-12-06 Carl Bechem Gmbh Lubrifiant à viscosité résiduelle réduite
WO2013192162A1 (fr) * 2012-06-20 2013-12-27 E. I. Du Pont De Nemours And Company Fluide et système de transfert thermique à basse température
US9382377B2 (en) 2011-08-10 2016-07-05 Basf Se Polymer mixtures as deposit inhibitors in water-bearing systems

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0916938A2 (fr) 1997-11-13 1999-05-19 Biophotonics Information Laboratories Ltd. Appareil de mesure optique
WO2005113702A1 (fr) 2004-05-21 2005-12-01 Basf Aktiengesellschaft Nouvelles paires de substances pour des pompes a chaleur a absorption, des machines frigorifiques a absorption et des transformateurs thermiques
WO2006087333A1 (fr) 2005-02-16 2006-08-24 Solvent Innovation Gmbh Machine de procede ou de travail dans laquelle le liquide de fonctionnement est un liquide ionique
WO2008043837A1 (fr) 2006-10-13 2008-04-17 Basf Se Liquides ioniques servant à solubiliser des polymères

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4926411B2 (ja) * 2005-04-08 2012-05-09 出光興産株式会社 グリース組成物
EP2473574A2 (fr) * 2009-09-03 2012-07-11 Basf Se Liquides ioniques dotés d'une viscosité améliorée

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0916938A2 (fr) 1997-11-13 1999-05-19 Biophotonics Information Laboratories Ltd. Appareil de mesure optique
WO2005113702A1 (fr) 2004-05-21 2005-12-01 Basf Aktiengesellschaft Nouvelles paires de substances pour des pompes a chaleur a absorption, des machines frigorifiques a absorption et des transformateurs thermiques
WO2006087333A1 (fr) 2005-02-16 2006-08-24 Solvent Innovation Gmbh Machine de procede ou de travail dans laquelle le liquide de fonctionnement est un liquide ionique
WO2008043837A1 (fr) 2006-10-13 2008-04-17 Basf Se Liquides ioniques servant à solubiliser des polymères

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012163550A1 (fr) * 2011-06-03 2012-12-06 Carl Bechem Gmbh Lubrifiant à viscosité résiduelle réduite
US9382377B2 (en) 2011-08-10 2016-07-05 Basf Se Polymer mixtures as deposit inhibitors in water-bearing systems
WO2013192162A1 (fr) * 2012-06-20 2013-12-27 E. I. Du Pont De Nemours And Company Fluide et système de transfert thermique à basse température

Also Published As

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EP2598593B1 (fr) 2014-04-23
WO2012016835A3 (fr) 2012-04-12
EP2598593A2 (fr) 2013-06-05
ES2469373T3 (es) 2014-06-18

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